U.S. patent number 7,968,632 [Application Number 11/921,750] was granted by the patent office on 2011-06-28 for polycarbonate resin composition and process for producing thereof.
This patent grant is currently assigned to Mitsubishi Engineering-Plastics Corporation. Invention is credited to Masayuki Akada, Seiichi Takada.
United States Patent |
7,968,632 |
Akada , et al. |
June 28, 2011 |
Polycarbonate resin composition and process for producing
thereof
Abstract
There is provided an antistatic polycarbonate resin composition
and molded product formed by melt-molding the said resin
composition, which resin composition has totally well balanced
excellent properties including heat resistance, in which yellow- or
brown-coloring can be prevented even though under melt-kneading
step, molding step and such a circumstance that it is used at high
temperature for long times, and the fluidity is improved without
notably deterioration of mechanical strengths and transparency. A
polycarbonate resin composition comprising 100 parts by weight of
polycarbonate resin, 0.1 to 5.0 parts by weight of phosphonium
sulfonate (A) represented by the following chemical formula (1),
0.1 to 10 parts by weight of aromatic polycarbonate resin oligomer
(B) and 0.01 to 8 parts by weight of caprolactone-based polymer
(C); and a molded product produced by melt-molding the said
polycarbonate resin.
Inventors: |
Akada; Masayuki (Hiratsuka,
JP), Takada; Seiichi (Hiratsuka, JP) |
Assignee: |
Mitsubishi Engineering-Plastics
Corporation (Tokyo, JP)
|
Family
ID: |
37532159 |
Appl.
No.: |
11/921,750 |
Filed: |
June 5, 2006 |
PCT
Filed: |
June 05, 2006 |
PCT No.: |
PCT/JP2006/311210 |
371(c)(1),(2),(4) Date: |
March 02, 2009 |
PCT
Pub. No.: |
WO2006/134797 |
PCT
Pub. Date: |
December 21, 2006 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
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US 20090186967 A1 |
Jul 23, 2009 |
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Foreign Application Priority Data
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|
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Jun 15, 2005 [JP] |
|
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2005-175250 |
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Current U.S.
Class: |
524/146; 524/158;
524/157 |
Current CPC
Class: |
C08L
69/00 (20130101); C08L 69/00 (20130101); C08L
2666/18 (20130101); C08L 67/04 (20130101); C08K
5/13 (20130101); C08K 5/50 (20130101); C08K
5/005 (20130101) |
Current International
Class: |
C08K
5/42 (20060101); C08K 5/5398 (20060101) |
Field of
Search: |
;524/146,157,158 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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63-128060 |
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May 1988 |
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JP |
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07-207138 |
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Aug 1995 |
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JP |
|
09-12859 |
|
Jan 1997 |
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JP |
|
09-194711 |
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Jul 1997 |
|
JP |
|
09 194711 |
|
Jul 1997 |
|
JP |
|
10-237293 |
|
Sep 1998 |
|
JP |
|
2003-26911 |
|
Jan 2003 |
|
JP |
|
Other References
International Search Report mailed Jul. 11, 2006. cited by
other.
|
Primary Examiner: Szekely; Peter
Attorney, Agent or Firm: Nixon & Vanderhye P.C.
Claims
The invention claimed is:
1. A transparent polycarbonate resin composition comprising 100
parts by weight of polycarbonate resin, 0.1 to 5.0 parts by weight
of phosphonium sulfonate (A) represented by the following chemical
formula (1), 0.5 to 1 parts by weight of aromatic polycarbonate
resin oligomer (B) and 0.01 to 8 parts by weight of
caprolactone-based polymer (C) ##STR00004## (where in the chemical
formula (1), R.sup.1 is an alkyl group or aryl group having a
carbon number of 1 to 40, which may have substituent group(s) and
R.sup.2 to R.sup.5 are independently hydrogen atom, or an alkyl
group or aryl group having a carbon number of 1 to 10 wherein each
R.sup.2 to R.sup.5 may be same group or different group.)
2. A transparent polycarbonate resin composition according to claim
1, wherein the total blending amount of aromatic polycarbonate
resin oligomer (B) and caprolactone-based polymer (C) based on 100
parts by weight of polycarbonate resin (B+C) is 1.0 to 7 parts by
weight.
3. A transparent polycarbonate resin composition according to claim
1, further comprising a phosphorus-based stabilizer (D) in an
amount of 0.01 to 1.0 parts by weight based on 100 parts by weight
of polycarbonate resin.
4. A transparent polycarbonate resin composition according to claim
1, further comprising a phenol-based antioxidant (E) having a
structure in the molecule represented by the following chemical
formula (2) in an amount of 0.01 to 1.0 parts by weight based on
100 parts by weight of polycarbonate resin. ##STR00005## (where in
the chemical formula (2), R.sup.6 to R.sup.8 are independently
hydrogen atom or an alkyl group having a carbon number of 1 to 3
and t-Bu is a tert-butyl group.)
5. A transparent polycarbonate resin composition according to claim
1, further comprising a weather resistant improver (F) in an amount
of 0.01 to 3.0 parts by weight based on 100 parts by weight of
polycarbonate resin.
6. A transparent molded product produced by melt-molding the
polycarbonate resin composition according to claim 1.
Description
This application is the U.S. national phase of International
Application No. PCT/JP2006/311210 filed 5 Jun. 2006 which
designated the U.S. and claims priority to JP 2005-175250 filed 15
Jun. 2005, the entire contents of each of which are hereby
incorporated by reference in their entirety.
TECHNICAL FIELD
The present invention relates to a antistatic-polycarbonate resin
composition, and more particularly it relates to a polycarbonate
resin composition having totally well balanced excellent properties
and molding products formed by melt-molding the said resin
composition.
BACKGROUND ART
Since polycarbonate resins are excellent in mechanical strength,
heat resistance, transparency or the like, the resins are widely
used in fields of materials of electronic/electric/OA equipments,
automobile parts, construction materials, medical appliances,
sundry articles or the like. However, since polycarbonate resins
has a high surface resistance value, it is difficult to eliminate
the static charge generated by contact and friction. Therefore,
polycarbonate resins have such problems that waste and dust are
attached on the surface of molded product to deteriorate the
appearance and transparency, electric shock causes discomfort of
human body, noise generates and improper operating signals for a
machine are produced. From these, it is demanded to provide a
polycarbonate resin composition and molding products formed by
melt-molding the said resin composition which have antistatic
property by reducing the surface resistance value of polycarbonate
resin without deterioration of polycarbonate resin properties in
nature.
Generally, as the polycarbonate resin composition having antistatic
property, there has been proposed a resin composition comprising
polycarbonate resin, phosphonium sulfonate, phosphite and
caprolactone-based polymer which are blended (refer to Japanese
Patent Application Laid-open (KOKAI) No. H09-194711). However, the
said resin composition has such problems that fluidity variation is
large so that stable molding is difficult, yellow or brown coloring
generates during the melt-kneading step and molding step, and the
mechanical strength and antistatic property are deteriorated. It is
thought that these problems are caused by high melt viscosity of
polycarbonate resin so that the melt-kneading temperature and
melt-molding temperature rise and the thermal decomposition of
resin notably generates.
There have been also proposed a polycarbonate resin molded product
for optical use comprising a polycarbonate resin and 1 to 60% by
weight of polycarbonate oligomer blended (refer to Japanese Patent
Application Laid-open (KOKAI) No. S61-123658), and a resin
comprising a polycarbonate resin and 10% by weight or more of
polycarbonate oligomer having a molecular weight of 2000 to 5000
(refer to Japanese Patent Application Laid-open (KOKAI) No.
H09-208684). However, these proposals only suggest that the
fluidity is affected by blending oligomer when using the molding
products for optical arts.
In the above prior arts, when the fluidity of resin composition
having antistatic property is improved, the color hue and
mechanical strengths tend to deteriorate notably. Therefore, it is
desired to provide an antistatic polycarbonate resin composition
and molded product formed by melt-molding the said resin
composition, which resin composition has totally well balanced
excellent properties including heat resistance, in which yellow- or
brown-coloring can be prevented even though under melt-kneading
step, molding step and such a circumstance that it is used at high
temperature for long times, and the fluidity is improved without
notably deterioration of mechanical strengths and transparency.
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
An object of the present invention is to provide an antistatic
polycarbonate resin composition and molded product formed by
melt-molding the said resin composition, which resin composition
has totally well balanced excellent properties including heat
resistance, in which yellow- or brown-coloring can be prevented
even though under melt-kneading step, molding step and such a
circumstance that it is used at high temperature for long times,
and the fluidity is improved without notably deterioration of
mechanical strengths and transparency.
Means for Solving the Problem
As the result of present inventors' earnest studies, it has been
found that by blending an aromatic polycarbonate resin oligomer (B)
and caprolactone-based polymer (C) into a resin composition
comprising a polycarbonate resin and phosphonium sulfonate (A)
blended in each specific amount, a molded product having well
balanced excellent properties, in which coloring (change of color
hue) can be prevented in the melt-kneading step and molding step,
and the fluidity can be improved without deterioration of
mechanical strengths and transparency. The present invention has
been attained on the basis of the above finding.
Especially, in consideration of heat resistance, it is unexpected
finding to control the blending amount of caprolactone-based
polymer to the specific amount or less.
Thus, in aspects of the present invention, there is provided a
polycarbonate resin composition comprising 100 parts by weight of
polycarbonate resin, 0.1 to 5.0 parts by weight of phosphonium
sulfonate (A) represented by the following chemical formula (1),
0.1 to 10 parts by weight of aromatic polycarbonate resin oligomer
(B) and 0.01 to 8 parts by weight of caprolactone-based polymer
(C).
##STR00001## (where in the chemical formula (1), R.sup.1 is an
alkyl group or aryl group having a carbon number of 1 to 40, which
may have substituent group(s) and R.sup.2 to R.sup.5 are
independently hydrogen atom, or an alkyl group or aryl group having
a carbon number of 1 to 10 wherein each R.sup.2 to R.sup.5 may be
same group or different group); and a molded product produced by
melt-molding the said polycarbonate resin.
EFFECT OF THE INVENTION
According to the present invention, there can be obtained an
antistatic polycarbonate resin composition and molded product
formed by melt-molding the said resin composition, which resin
composition has totally well balanced excellent properties
including heat resistance, in which yellow- or brown-coloring can
be prevented even though under melt-kneading step, molding step and
such a circumstance that it is used at high temperature for long
times, and the fluidity is improved without notably deterioration
of mechanical strengths and transparency.
PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION
The present invention is described in detail below.
Polycarbonate Resin:
As the polycarbonate resin used in the present invention, there can
be used an aromatic polycarbonate, aliphatic polycarbonate,
aromatic-aliphatic polycarbonate or the like. Of these, an aromatic
polycarbonate is preferred. The aromatic polycarbonate is a resin
obtained by interfacial polymerization comprising reacting an
aromatic hydroxyl compound or an aromatic hydroxyl compound and a
small amount of polyhydroxyl with phosgene compound (phosgene
method), or melting method comprising reacting an aromatic hydroxyl
compound or an aromatic hydroxyl compound and a small amount of
polyhydroxyl with diester carbonate (ester exchange method). The
obtained polymer is a linear or branched thermoplastic polymer or
copolymer. Further, the aromatic polycarbonate resin is a resin
produced by melting method, whose amount of end OH group has been
controlled.
As the aromatic dihydroxyl compound, there are exemplified
2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethyl
bisphenol A, (4-hydroxyphenyl)-P-diisopropyl benzene, hydroquinone,
resorcinol, 4,4-dihydroxydiphenyl or the like. Of these, bisphenol
A is preferred. Further, for the purpose of enhancing flame
retardancy further, there may be used a polymer or oligomer in
which one or more tetraalkyl phosphonium sulfonate is bonded to the
above aromatic dihydroxyl compound and/or a polymer or oligomer
having siloxane structure and phenolic hydroxyl groups at the both
end groups.
In order to obtain a branched aromatic polycarbonate resin, a part
of the above aromatic dihydroxyl compound is replaced the following
compound: a polyhydroxyl compound such as phloroglucin,
4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2,4,6-dimethyl-2,4,6-tri(4-
-hydroxyphenyl)heptane,
2,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-3,1,3,5-tri(4-hydroxypheny-
l)benzene and 1,1,1-tri(4-hydroxyphenyl)ethane,
3,3-bis(4-hydroxyaryl), oxyindole (=isatin bisphenol), 5-chloro
isatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin
bisphenol, or the like. The amount of these compounds used is 0.01
to 10 mol %, preferably 0.1 to 2 mol % based on the aromatic
dihydroxyl compound.
In order to control the molecular weight of polycarbonate resin,
mono-equivalent aromatic hydroxyl compound can be used. Examples of
mono-equivalent aromatic hydroxyl compound may include m- and
p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long
chain alkyl group substituted phenol, or the like.
The preferred polycarbonate resins used in the present invention
are polycarbonate resins derived from bisphenol A and aromatic
polycarbonate copolymers derived from bisphenol A and bisphenol A
and the other aromatic dihydroxyl compound. Further, two or more
resins may be used in mixture as the polycarbonate resin used in
the present invention.
The viscosity average molecular weight of polycarbonate resin which
is an equivalent measured in methylene chloride as a solvent at
25.degree. C. is preferable 13000 to 40000, more preferably 14000
to 30000, especially preferably 15000, 29000. When the viscosity
average molecular weight is less than 13000, the mechanical
strength such as the impact strength may be insufficient. When the
viscosity average molecular weight is more than 40000, the fluidity
may be reduced.
Phosphonium Sulfonate (A):
The phosphonium sulfonate (A) used in the present invention is used
for the purpose of imparting antistatic property and is represented
by the following chemical formula (1):
##STR00002##
Where in the chemical formula (1), R.sup.1 is an alkyl group or
aryl group having a carbon number of 1 to 40, which may have
substituent group(s) and R.sup.2 to R.sup.5 are independently
hydrogen atom, or an alkyl group or aryl group having a carbon
number of 1 to 10 wherein each R.sup.2 to R.sup.5 may be same group
or different group.
The phosphonium sulfonate (A) represented by the above chemical
formula (1) is blended to the polycarbonate resin in an amount of
0.1 to 5.0 parts by weight, preferably 0.5 to 4.5 parts by weight,
more preferably 1.0 to 4.0 parts by weight, especially preferably
1.5 to 3.5 parts by weight based on 100 parts by weight of
polycarbonate resin. When the blending amount of phosphonium
sulfonate (A) is less than 0.1 parts by weight, sufficient
antistatic effect may not be attained. When the blending amount of
phosphonium sulfonate (A) is more than 5.0 parts by weight, the
transparency and mechanical strength may be deteriorated and silver
streak and peeling off phenomenon may occur at the surface of
molded product so that these may cause appearance
deterioration.
In the above chemical formula (1), R.sup.1 is an alkyl group or
aryl group having a carbon number 1 to 40. In view of transparency,
heat resistance and compatibility to the polycarbonate resin, an
aryl group is preferred. Further, an alkylbenzene or
alkylnaphthalene substituted with an alkyl group having a carbon
number of 1 to 34, preferably 5 to 20, more preferably 10 to 15 is
more preferred. In the above chemical formula (1), R.sup.2 to
R.sup.5 are independently an alkyl group or aryl group having a
carbon number 1 to 10. Preferred is an alkyl group having a carbon
number of 2 to 8, more preferably an alkyl group having a carbon
number of 3 to 6, especially preferably butyl group.
Examples of the phosphonium sulfonate (A) according to the present
invention may include tetrabutyl phosphonium dodecylsulfonate,
tetrabutyl phosphonium dodecylnebenzene sulfonate, trioctyl
phosphonium dodecylnebenzene sulfonate, tetraoctyl phosphonium
dodecylnebenzene sulfonate, tetraethyl phosphonium octadecylbenzene
sulfonate, tetraethyl phosphonium dibutylbenzene sulfonate,
tributylmethyl phosphonium dibutylbenzene sulfonate, triphenyl
phosphonium dinaphthyl sulfonate, trioctylmethyl phosphonium
diisopropylnaphthyl sulfonate, or the like. Of these, tetrabutyl
phosphonium dodecylnebenzene sulfonate is preferred in view of good
compatibility to polycarbonate resin and easy availability.
Aromatic Polycarbonate Oligomer (B)
The polycarbonate resin composition according to the present
invention is characterized in that the aromatic polycarbonate
oligomer (B) is contained in a specific amount in addition to the
phosphonium sulfonate (A). By this blending, it can be attained to
obtain a molded product having totally balanced good properties
such as transparency, coloring during the melt-kneading step and
molding step, fluidity, heat resistance, mechanical strength and
antistatic property.
In the present invention, the aromatic polycarbonate oligomer (B)
means an oligomer having a viscosity average molecular weight of
1000 to 10000. In view of attaining the improving effect of
fluidity while maintaining the balance for the other properties
such as impact resistance and transparency, the viscosity average
molecular weight thereof is preferably 1500 to 9000, more
preferably 2000 to 8000. When the viscosity average molecular
weight of oligomer is less than 1000, the oligomer may be easily
bled out from the molding product at the molding step. When the
viscosity average molecular weight of oligomer is more than 10000,
the fluidity may be deteriorated.
The number average polymerization degree (average of number of
repeating unit) of aromatic polycarbonate oligomer (B) is usually 2
to 15, preferably 3 to 4, more preferably 4 to 13. When the number
average polymerization degree thereof is 1, the oligomer may be
easily bled out from the molding product at the molding step. When
the number average polymerization degree thereof is more than 15,
the fluidity may be deteriorated.
The aromatic polycarbonate oligomer (B) can be produced by reacting
the aromatic dihydroxyl compound with phosgene or diester carbonate
in the presence of molecular weight controlling agent. As the
aromatic dihydroxyl compound, the above mentioned aromatic
dihydroxyl compound for the material of aromatic polycarbonate
resin mat be used, and bisphenol A is preferably used. As the
molecular weight controlling agent, there may be used the above
mentioned mono-equivalent aromatic hydroxyl compound used for
controlling the molecular weight of aromatic polycarbonate resin,
such as m- and p-methylphenol, m-and p-propylphenol,
p-tert-butylphenol, p-long chain alkyl group substituted phenol, or
the like.
As the aromatic polycarbonate oligomer (B), there may be used an
oligomer obtained by copolymerizaion using two or more aromatic
hydroxyl compounds. As the combination of aromatic hydroxyl
compounds, there may be exemplified bisphenol A (BPA) and
tetrabromobisphenol A (TBA).
The blending amount of aromatic polycarbonate oligomer (B) is 0.1
to 10 parts by weight, preferably 0.3 to 5 parts by weight, more
preferably 0.5 to 3 parts by weight based on 100 parts by weight of
polycarbonate resin. When the blending amount of aromatic
polycarbonate oligomer (B) is less than 0.1 parts by weight, the
improving effect of fluidity may be insufficient. When the blending
amount of aromatic polycarbonate oligomer (B) is more than 10 parts
by weight, the color hue after the thermal aging treatment may be
deteriorated and the impact strength may be reduced.
Further, in order to attain the improving effect of fluidity, the
blending ratio of aromatic polycarbonate oligomer (B) to the
phosphonium sulfonate (A) represented by the chemical formula (1)
((B)/(A), weight ratio) is usually 2/100 to 2000/100, preferably
5/100 to 500/100, more preferably 10/100 to 200/100.
Caprolactone-based Polymer (C):
In the resin composition according to the present invention, it is
featured to further blend the caprolactone-based polymer (C) in a
specific amount. The caprolactone-based polymer (C) in the present
invention is a polymer or copolymer having a constitutional unit
derived from .epsilon.-caprolactone in an amount of not less than
70% by weight, preferably 75% by weight, more preferably 80% by
weight in a molecule. As the monomer coplymerizable with from
.epsilon.-caprolactone, there may be exemplified lactone monomers
such as .beta.-propiolactone, pivalolactone and butylolactone,
alkylene oxides such as ethylene oxide, 1,2-propylene oxide,
1,3-propylene oxide and tetrahydrofuran, unsaturated monomers such
as styrene, methylmethacrylate and butadiene, coupling agents such
as dimethyl terephthalate and diphenyl carbonate.
As the caprolactone-based polymer (C), a partial hydrogen of
methylene chain in the .epsilon.-caprolactone unit may be
substituted with a halogen atom or hydrocarbon group. Further, the
end groups of caprolactone-based polymer may be modified by
esterification, etherfication or the like. As the production method
of caprolactone-based polymer is not limited. Usually, a method
comprising conducting ring-opening polymerization of
.epsilon.-caprolactone in the presence of suitable initiator such
as alcohol, glycol and water and catalyst such as titanium
tetrabutoxide and tin chloride is used.
The blending amount of caprolactone-based polymer (C) is 0.01 to 8
parts by weight based on 100 parts by weight of polycarbonate
resin. When the blending amount of caprolactone-based polymer (C)
is less than 0.01 parts by weight, the preventing effect of
coloring may be insufficient. When the blending amount of
caprolactone-based polymer (C) is more than 8 parts by weight, the
heat resistance, antistatic resistance and transparency may be
deteriorated. The blending amount of caprolactone-based polymer (C)
is preferably 0.05 to 5 parts, more preferably 0.08 to 4 parts by
weight, especially preferably 0.1 to 3 parts by weight based on 100
parts by weight of polycarbonate resin.
In order to prevent coloring at the molding step, the blending
ratio of caprolactone-based polymer (C) to the phosphonium
sulfonate (A) represented by the chemical formula (1) ((C)/(A),
weight ratio) is usually 1/20 to 20/1, preferably 1/10 to 10/1,
more preferably 1/8 to 5/1, especially preferably 1/7 to 1/1.
Further, in order to maintain the balance of impact resistance and
heat resistance, the blending ratio of aromatic polycarbonate
oligomer (B) to the caprolactone-based polymer (C) ((B)/(C), weight
ratio) is usually 1/20 to 20/1, preferably 1/10 to 10/1, more
preferably 1/8 to 5/1, especially preferably 1/4 to 4/1.
Still further, in order to maintain the balance of impact
resistance and heat resistance, the total amount of aromatic
polycarbonate oligomer (B) and caprolactone-based polymer (C)
((B)+(C)) is usually 0.11 to 18 parts by weight, preferably 0.1 to
10 parts by weight, more preferably 0.5 to 7 parts by weight,
especially preferably 1.0 to 3.0 parts by weight based on 100 parts
by weight of polycarbonate resin.
The number average molecular weight of caprolactone-based polymer
(C) (measured by GPC) is preferably 1000 to 100000. When the number
average molecular weight is less than 1000, the thermal stability
may be insufficient. When the number average molecular weight is
more than 100000, the processability and transparency may be
deteriorated. In view of good transparency, the number average
molecular weight of caprolactone-based polymer (C) is more
preferably 5000 to 50000, still more preferably 10000 to 30000.
When using caprolactone-based polymer (C) having a large molecular
weight, the resin composition may be whitened. It is thought that
such whitening is caused by a difference of refractive indexes
between sea phase and island phase in a sea/island structure formed
by dispersing domains comprising caprolactone-based polymer into
the matrix. In order to prevent the whitening and improve the
transparency, it is preferred to conduct the esterification
reaction between the polycarbonate resin and caprolactone-based
polymer (C). Therefore, it is preferred that an esterexchange
catalyst is blended into the resin composition and the composition
is kneaded.
Concrete examples of esterexchange catalyst may include acid
materials such as p-toluenesulphonic acid, trifluoroacetic acid,
inorganic acids and Lewis acids such as boron trifluoride; metal
salts such as acetic acid salt of alkaline metal or alkaline earth
metal; and compounds of zinc, manganese, cobalt, antimony,
germanium, titanium and tin. Of these, zinc, antimony, titanium and
tin compounds are preferred. Concretely, tetraalkyltitanate, zinc
acetate, stannous acetate and antimony trioxide are more preferred.
Although using no catalyst, there may be a case capable of
proceeding the esterexchange reaction. However, in order to proceed
the esterexchange reaction more surely, the amount of esterexchange
catalyst blended is preferably 0.001 to 0.2 parts by weight based
on 100 parts by weight of polycarbonate resin. When the blending
amount of esterexchange catalyst is less than 0.001 parts by
weight, acceleration effect of esterexchange reaction may be
insufficient. When the blending amount of esterexchange catalyst is
more than 0.2 parts by weight, coloring of composition may occur.
The blending amount of esterexchange catalyst is more preferably
0.005 to 0.1 parts by weight, still more preferably 0.004 to 0.08
parts by weight.
Phosphorus-based Stabilizer (D)
In the present invention, it is preferred to blend a
phosphorus-based stabilizer (D) into the polycarbonate resin
composition in a specific amount so that the thermal stability can
be improved. As the phosphorus-based stabilizer (D), there are
exemplified phosphorous acid, phosphoric acid, phosphites,
phosphates or the like. Of these, phosphorous acid esters such as
phosphites and phosphonites are preferred in view of containing a
trivalent phosphorus and being effective for preventing the change
of color.
Examples of the above phosphite may include triphenylphosphite,
tris(nonylphenyl)phosphite, dilaurylhydrogenphosphite,
triethylphosphite, tridecylphosphite, tris(2-ethylhexyl)phosphite,
tris(tridecyl)phosphite, tristearylphosphite,
diphenylmonodecylphosphite, monophenyldidecylphosphite,
diphenylmono(tridecyl)phosphite, tetraphenyl dipropyleneglycol
diphosphite, tetraphenyl tetra(tridecyl)pentaerythritol
tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer,
diphenylhydrogenphosphite,
4,4'-butylydene-bis(3-methyl-6-tert-butylphenyl
di(tridecyl)phosphite, tetra(tridecyl)-4,4'-isopropylydene
diphenylphosphite, bis(tridecyl)pentaerythritol diphosphite,
bis(nonylphenyl)pentaerythritol diphosphite,
dilaurylpentaerythritol diphosphite, distearylpentaerythritol
diphosphite, tris(4-tert-butylphenyl)phosphite,
tris(2,4-di-tert-butylphenyl)phosphite, hydrogenated bisphenol A
pentaerithritol phosphite polymer, bis(2,4-di-t-butylphenyl)
pentaerithritol phosphite, bis(2,6-di-t-butyl-4-methyl phenyl)
pentaerithritol phosphite,
2,2'methylenebis(4,6-di-tert-butylphenyl)octyl phosphite,
bis(2,4-di-cumylphenyl) pentaerithritol diphosphite, or the
like.
Examples of the above phosphonites may include
tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite,
tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite,
tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,
tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite,
tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite,
or the like.
Examples of the above acid phosphate may include methyl acid
phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl
butyl acid phosphate, butoxy acid phosphate, octyl acid phosphate,
2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid
phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl
acid phosphate, phenyl acid phosphate, nonyl acid phosphate,
cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy
polyethylene glycol acid phosphate, bisphenol A acid phosphate,
dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid
phosphate, diisopropyl acid phosphate, dibutyl acid phosphate,
dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl
acid phosphate, dilauryl acid phosphate, distearyl acid phosphate,
diphenyl acid phosphate, bis-nonylphenyl acid phosphate, or the
like.
As the phosphorous acid esters in the phosphorus-based stabilizer
(D), distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-t-butyl-4-methyl
phenyl) pentaerithritol phosphite,
2,2'methylenebis(4,6-di-tert-butylphenyl)octyl phosphite and
bis(2,4-di-cumylphenyl) pentaerithritol diphosphite are preferred.
In view of excellent thermal stability and difficult to be
hydrolyzed, tris(2,4-di-tert-butylphenyl)phosphite is especially
preferred.
Two or more phosphorus-based stabilizer (D) may be blended in
mixture. The blending amount of phosphorus-based stabilizer (D) is
usually 0.01 to 1.0 parts by weight, preferably 0.03 to 0.5 parts
by weight, more preferably 0.05 to 0.2 parts by weight based on 100
parts by weight of polycarbonate resin. When the blending amount of
phosphorus-based stabilizer (D) is less than 0.01 parts by weight,
the effect of stabilizer may be insufficient so that there is a
tendency to reduce the molecular weight during the molding and
deteriorate the color hue. When the blending amount of
phosphorus-based stabilizer (D) is more than 1.0 part by weight,
there is a tendency to generate a silver and deteriorate the color
hue more because of excess blending amount.
The blending ratio of phosphorus-based stabilizer (D) to the
phosphonium sulfonate (A) represented by the chemical formula (1)
((D)/(A), weight ratio) is usually 0.5/100 to 50/100, preferably
1/100 to 20/100, more preferably 2/100 to 15/100. Further, in order
to prevent the thermal deterioration during the molding, the
blending ratio of phosphorus-based stabilizer (D) to the aromatic
polycarbonate oligomer (B) ((D)/(B), weight ratio) is usually
0.1/100 to 1000/100, preferably 1/100 to 200/100, more preferably
2/100 to 40/100.
Further, in order to prevent the thermal deterioration during the
molding, the blending ratio of phosphorus-based stabilizer (D) to
the caprolactone-based polymer (C) ((D)/(C), weight ratio) is
usually 1/500 to 3/1, preferably 1/100 to 1/1, more preferably 1/15
to 1/3.
Phenol-based Antioxidant (E):
In the present invention, it is preferred to further blend a
phenol-based antioxidant (E) in a specific amount so as to improve
the preventing effect of deterioration of mechanical strength,
transparency and color hue of polycarbonate resin composition.
Among the phenol-based antioxidant (E) used in the present
invention, it is preferred to use the phenol-based antioxidant
having a specific structure represented by the following chemical
formula (2) in the molecule so as to prevent the deterioration of
color hue and improve the mechanical strength while maintaining the
fluidity, transparency and antistatic property.
##STR00003## Where in the chemical formula (2), R.sup.6 to R.sup.8
are independently hydrogen atom or an alkyl group having a carbon
number of 1 to 3 and t-Bu is a tert-butyl group.)
R.sup.6 to R.sup.8 in the chemical formula (2) are groups which is
not bulkier than tert-butyl group and are independently hydrogen
atom or an alkyl group having a carbon number of 1 to 3. In the
present invention, it is important that the stereo condition around
the hydroxyl group is not bulky. Therefore, R.sup.6 to R.sup.8 are
preferably linear alkyl groups, more preferably groups having the
carbon number of two or less, still more preferably methyl group or
hydrogen atom.
Further, in view of enhancing the antioxidant effect, substituents
R.sup.6 and/or R.sup.7 are preferably hydrogen atom or alkyl group
having the carbon number of 1 to 3.
As concrete examples of phenol-based antioxidant having the
specific structure represented by the chemical formula (2), there
may be mentioned 2,2'-methylenebis(4-methyl-6-tert-butylphenol),
4,4'-butylidenebis(6-tert-butyl-3-methylphenol),
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene
glycolbis[.beta.-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate],
1,6-hexanediolbis[.beta.-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionat-
e],
pentaerithritol-tetrakis[.beta.-(3-tert-butyl-4-hydroxy-5-methylphenyl-
)propionate],
octadecyl[.beta.(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate],
or the like.
In view of requirement of heat resistance during the kneading with
the polycarbonate, among the above phenol-based antioxidants,
4,4'-butylidenebis(6-tert-butyl-3-methylphenol),
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane and
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane are preferred.
Especially, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane
and
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
Two or more phenol-based antioxidants (E) may be used. The blending
amount of phenol-based antioxidants (E) is usually 0.01 to 1.0
parts by weight, preferably. 0.03 to 0.5 parts by weight, more
preferably 0.05 to 0.2 parts by weight based on 100 parts by weight
of polycarbonate resin. When the blending amount of phenol-based
antioxidants (E) is less than 0.01 parts by weight, the effect of
antioxidant may be insufficient. When the blending amount of
phenol-based antioxidants (E) is more than 1.0 part by weight,
there is a tendency to generate a silver streak and deteriorate the
color hue because of excess blending amount.
The blending ratio of phenol-based antioxidants (E) to the
phosphonium sulfonate (A) represented by the chemical formula (1)
((E)/(A), weight ratio) is usually 0.5/100 to 50/100, preferably
1/100 to 20/100, more preferably 2/100 to 15/100. Further, in order
to prevent the thermal deterioration during the molding, the
blending ratio of phenol-based antioxidants (E) to the aromatic
polycarbonate oligomer (B) ((E)/(B), weight ratio) is usually
0.1/100 to 1000/100, preferably 1/100 to 200/100, more preferably
2/100 to 40/100. Still further, in order to prevent the thermal
deterioration during the molding, the blending ratio of
phenol-based antioxidants (E) to the caprolactone-based polymer (C)
((E)/(C), weight ratio) is usually 1/100 to 3/1, preferably 1/40 to
1/1, more preferably 1/15 to 1/2.
In the present invention, by blending the phenol-based antioxidants
(E) together with the phosphorus-based stabilizer (D) in
combination into the resin composition, there can be attained
remarkable technical effects in improvement of mechanical strength,
transparency and color hue of the polycarbonate resin composition
having antistatic property. The blending ratio of phenol-based
antioxidants (E) to the phosphorus-based stabilizer (D) ((E)/(D),
weight ratio) is 25/100 to 250/100, preferably 50/100 to 200/100,
more preferably 75/100 to 125/100.
Weather Resistant Improver (F):
In the present invention, for the purpose of improving the weather
resistant of polycarbonate resin composition, it is preferred to
further blend a weather resistant improver (F). As the weather
resistant improver (F), compounds generally known as UV absorbers
and light stabilizers nay be used. As the act of these compounds,
there are proposed a mechanism that they absorb light energy of
visual light and UV light and convert the light energy to thermal
energy; a mechanism that generated precursors are detoxified by
photochemistry action.
As the weather resistant improver (F), there may be mentioned
various type compounds such as benzophenone-based,
benzotriazol-based, salicylic ester-based, benzoate-based,
triazine-based, hindered amine-based and cynnamyl-based compounds.
These weather resistant improvers may used singly or as a mixture
of two or more.
As the benzophenone-based compounds, there may be exemplified
2,4-dihydroxybenzophenone, 2-4-methoxybenzophenone,
2-hydroxy-4-octyloxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone,
2-hydroxy-4-octadecyloxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate and
bis(2-hydroxy-3-benzoyl-6-methoxyphenyl)methane.
As the benzotriazol-based compounds there may be exemplified
2-(2-hydroxy-5-methylphenyl)-2H-benzotriazol,2-(2-hydroxy-3,5-di-t-butylp-
henyl)-2H-benzotriazol,
2-(2-hydroxy-3-t-butyl-5-methylphenyl)-2H-benzotriazol,
2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazol,
2-(3,5-di-t-octyl-2-hydroxyphenyl)-2H-benzotriazol,
2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazol,
2-(3-lauryl-5-methyl-2-hydroxyphenyl)-2H-benzotriazol,
2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazol,2-(3-t-butyl--
5-methyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazol,
2-(3,5-bis(1-methyl-1-phenylethyl)-2-hydroxyphenyl)-2H-benzotriazol,
bis(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-methylphenyl)methane,
bis(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl-
)methane,
bis(3-2H-benzotriazol-2-yl)-2-hydroxy-5-cumylphenyl)methane,
bis(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-octylphenyl)methane,
1,1-bis(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-methylphenyl)octane,
1,1-bis(3-(2H-5-chlorobenzotriazol-2-yl)-2-hydroxy-5-methylphenyl)octane,
1,2-ethanediylbis(3-(2H-benzotriazol-2-yl)-2-hydroxybenzoate),
1,12-dodecanediylbis(3-(2H-benzotriazol-2-yl)-4-hydroxybenzoate),
1,3-cyclohexanediylbis(3-(5-chloro-2H-benzotriazol-2-yl)-2-hydroxybenzoat-
e),
1,4-butanediylbis(3-(2H-benzotriazol-2-yl)-4-hydroxy-5-methylethylphen-
ylethanoate),
3,6-dioxa-1,8-octanediylbis(3-(5-methoxy-2H-benzotriazol-2-yl)-4-hydroxyp-
henyethanoate),
1,6-hexanediylbis(3-(3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl)p-
ropionate),
p-xylenediylbis(3-(3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl)propionate),
bis(3-(2H-benzotriazol-2-yl)-4-hydroxytoluyl)malonate,
bis(2-(3-(2H-benzotriazol-2-yl)-4-hydroxy-5-octylphenyl)ethyl)terephthala-
te,
bis(3-(2H-benzotriazol-2-yl)-4-hydroxy-5-propyltoluyl)octadionate,
2-(2H-benzotriazol-2-yl)-6-phthalimidemethyl-4-methylphenol,
2-(2H-benzotriazol-2-yl)-6-phthalimideethyl-4-methylphenol,
2-(2H-benzotriazol-2-yl)-6-phthalimideoctyl-4-methylphenol,
2-(2H-benzotriazol-2-yl)-6-phthalimidemethyl-4-t-butylphenol,
2-(2H-benzotriazol-2-yl)-6-phthalimidemethyl-4-cumylphenol,
2-(2H-benzotriazol-2-yl)-4,6-bis(phthalimidemethyl)phenol, or the
like.
As the salicylic ester-based compounds there may be exemplified
phenylsalicylate,
2,4-di-tert-butylphenyl-3,5-do-tert-butyl-4-hydroxybenzoate, or the
like.
As the benzoate-based compounds there may be exemplified
2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, or the
like.
As the triazine-based compounds there may be exemplified
2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, or the
like.
As the hindered amine-based compounds there may be exemplified
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butylmalonate,
dimethylsuccinate.1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperid-
ine condensation product,
poly((6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl)((2,2,6,6-
-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperi-
dyl)imino)),N,N'-bis(3-aminopropyl)ethylenediamine.2,4-bis(N-butyl-N(1,2,2-
,6,6-pentamethyl-4-piperidyl)amino)-6-chloro-1,3,5-triazine
condensation product,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarb-
oxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracar-
boxylate, or the like.
As the other weather resistant improvers, there are exemplified
2-ethoxy-2'-ethyl-oxalic acid bisanilide,
ethyl-2-cyano-3,3-diphenylacrylate,2-ethylhexyl-2-cyano-3,3'-diphenylacry-
late.
Among the above weather resistant improvers, in view of good
compatibility to the polycarbonate resin and being lightly affected
to the properties, the benzotriazole-based compounds are preferred.
Further, among the benzotriazole-based compounds,
2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazol,
bis(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl-
)methane,
bis(3-2H-benzotriazol-2-yl)-2-hydroxy-5-cumylphenyl)methane and
2-(3,5-bis(1-methyl-1-phenylethyl)-2-hydroxyphenyl)-2H-benzotriazol
are preferred, and 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazol is
especially preferred.
The blending amount of weather resistant improver (F) is usually
0.01 to 3.0 parts by weight, preferably 0.03 to 1.0 parts by
weight, more preferably 0.1 to 0.8 parts by weight based on 100
parts by weight of polycarbonate resin. When the blending amount of
weather resistant improver (F) is less than 0.01 parts by weight,
the effect of weather resistant improving may be insufficient. When
the blending amount of weather resistant improver (F) is more than
3.0 part by weight, there is a tendency to generate contamination
of molding during the injection molding. The above weather
resistant improver may be blended thereinto singly or in a mixture
of two or more.
The blending ratio of weather resistant improver (F) to the
aromatic polycarbonate oligomer (B) ((F)/(B), weight ratio) is
usually 0.1/100 to 3000/100, preferably 1/100 to 300/100, more
preferably 3/100 to 160/100. The blending ratio of weather
resistant improver (F) to the caprolactone-based polymer (C)
((F)/(C), weight ratio) is usually 1/50 to 5/1, preferably 1/20 to
2/1, more preferably 1/10 to 1/1. The blending ratio of weather
resistant improver (F) to the phenol-based antioxidants (E)
((F)/(E), weight ratio) is usually 0.1 to 20, preferably 0.5 to 10,
more preferably 1.0 to 5.0.
Into the antistatic polycarbonate resin composition according to
the present invention, the other additives imparting desired
properties therein may be added within the scope of the present
invention. As the additives, there may be exemplified the other
polymers, flame retardants, impact resistance improvers,
plasticizers, mold releasing agents, lubricants, compatibilizers,
colorants (pigments such as carbon black and titanium oxide, and
dyes such as bluing agents), reinforcing agents or fillers such as
glass fibers, glass beads, glass flakes, carbon fiber, fibrous
magnesium, potassium titanate whisker, ceramic whiskers, mica,
talc, clay and calcium silicate, or the like. These may be blended
singly or in a mixture of two or more.
Among the above additives, in order to preventing coloring
effectively, it is preferred to blend the bluing agent (G) such as
DIARESIN BLUE G manufactured by Mitsubishi Chemical Corporation,
preferably anthraquinone-based bluing agents MACROLEX BLUE RR
manufactured by Bayer AG, MACROLEX BLUE 3R manufactured by Bayer AG
and MACROLEX VIOLET 3R manufactured by Bayer AG.
As the process for producing the polycarbonate resin composition
according to the present invention, there may be exemplified a
method comprising blending the above mentioned phosphonium
sulfonate (A), aromatic polycarbonate resin oligomer (B),
caprolactone-based polymer (C) and if required, phosphorus-based
stabilizer (D), phenol-based antioxidants (E) and weather resistant
improver (F) into the polycarbonate resin at the optional stage
before the melt-molding stage to obtain the final molded product by
known methods by the skilled person in the art, and kneading
it.
As the blending method, there are exemplified a method using a
tumbler, Henschel mixer, super mixer or the like, a method of
feeding and mixing a quantitative amount of materials by a feeder
to an extruder hopper, or the like. As the kneading method, there
are exemplified a method using a single-screw extruder and a method
using a twin-screw extruder. In order to enhance the dispersibility
of antistatic agent therein, the method using a twin-screw extruder
is preferred.
Further, since case by case, the phosphonium sulfonate (A)
(antistatic agent) used in the present invention is a tenacious
liquid at room temperature, it may be added to an extruder by the
following methods. (1) A method comprising warming the phosphonium
sulfonate (A) moderately to reduce the viscosity thereof, blending
the phosphonium sulfonate (A) with the polycarbonate resin,
aromatic polycarbonate resin oligomer, caprolactone-based polymer
and the other stabilizers by use of a super mixer to obtain a
mixture and feeding the mixture into an extruder. (2) A method
comprising warming the phosphonium sulfonate (A) moderately to
reduce the viscosity thereof and feeding the phosphonium sulfonate
(A) into an extruder directly by use of a liquid feeding equipment.
In this method, the constitutional components other than the
phosphonium sulfonate (A) had been prior blended and the blended
mixture is kneaded with the liquidfied antistatic agent in the
extruder. (3) A method comprising warming the phosphonium sulfonate
(A) moderately to reduce the viscosity thereof and prepare a master
agent comprising the phosphonium sulfonate (A) and a part of
polycarbonate resin. Thereafter, the remained polycarbonate resin,
aromatic polycarbonate resin oligomer, caprolactone-based polymer
and the other necessary additives are added into the master agent
to obtain a full blended mixture and it is fed into an
extruder.
A method of melt-molding using the polycarbonate resin composition
according to the present invention to obtain a molded product is
not limited and general melt-molding methods used for general
thermoplastic resin compositions such as injection molding may be
used. In addition, if required, various types injection molding
methods such as gas-assist molding, foaming molding, injection blow
molding, high-speed injection molding, injection compression
molding, insert molding, in-mold coating molding, coinjection
molding, sandwiched molding, heat insulation-mold molding, rapid
quenching and rapid heating-mold molding, or the like. As the molds
used in the above various types injection molding methods, the
runner part may comprise a cold runner or hot runner and these
runners may be selected for the purpose. Further, as melt-molding
methods other than the injection molding, there may be used blow
molding, extrusion molding for film or sheet preparation, profile
extrusion molding, thermoforming, rotation molding, or the
like.
The molded product obtained in the present invention has totally
well balanced excellent properties for the transparency, preventing
coloring during the melt-kneading and molding steps, fluidity, heat
resistance, mechanical strength and antistatic property. Therefore,
the molded product according to the present invention is suitably
used for substrates and cartridges of recording medium, various
parts of electronic & OA equipments, building materials such as
transparent sheets and transparent films, parts of miscellaneous
goods, parts of pinball machines (covers for circuits, chassis,
guides for a pinball, or the like), medical appliances, window
glasses, transparent parts for lightings or vehicles such as meter
covers, room lamps, taillight lenses, turning signals lamps and
head light lenses, further, suitably used for transparent parts for
lightings
EXAMPLES
The present invention is described in more detail by Examples.
However, it should be noted that the following Examples are only
illustrative and not intended to limit the scope of the present
invention. In the following Examples and Comparative Examples, all
"parts" are by weight unless otherwise noted. The materials used,
process for producing the polycarbonate resin composition and
molding methods thereof, and evaluation methods of products are
shown in the following.
Materials
(1) Aromatic Polycarbonate Resin:
"Iupiron.RTM. S-1000" produced by Mitsubishi Engineering-Plastics
Corporation, viscosity-average molecular weight of 26,000,
abbreviated as "PC-1" in the following Tables 1 to 3. (2)
Phosphonium sulfonate: "MEC-100" produced by Takemoto Oil & Fat
Co., Ltd, tetrabutyl phosphonium dodecylnebenzene sulfonate,
abbreviated as "Antistatic agent A-1" in the following Tables 1 to
3. (3) Aromatic polycarbonate oligomer: "PC Oligomer AL071"
produced by Mitsubishi Engineering-Plastics Corporation,
viscosity-average molecular weight of 5,000, abbreviated as
"Oligomer B-1" in the following Tables 1 to 3. (4)
Caprolactone-based Polymer: (C-1) "Placcel HIP" produced by Daicel
Chemical Industries, Ltd., number-average molecular weight of
10,000, abbreviated as "C-1" in the following Tables 1 to 3. (C-2)
"Placcel H5" produced by Daicel Chemical Industries, Ltd.,
number-average molecular weight of 50,000, abbreviated as "C-2" in
the following Tables 1 to 3. (C-3) "Placcel H7" produced by Daicel
Chemical Industries, Ltd., number-average molecular weight of
70,000, abbreviated as "C-3" in the following Tables 1 to 3. (5)
Phosphorus-based stabilizer: "ADK STAB 2112" produced by Adeka
Corporation, tris(2,4-di-tert-butylphenyl)phosphite, abbreviated as
"Phosphorus-based stabilizer D-1" in the following Tables 1 to 3.
(6) Phenol-based antioxidant: "ADK STAB AO-80" produced by Adeka
Corporation,
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, abbreviated as
"Antioxidant E-1" in the following Tables 1 to 3. (7) Weather
resistant improver: "SEESORB709" produced by Shipro Kasei Kaisha,
Ltd., benzotriazol-based UV absorber,
2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazol, abbreviated as
"Weather resistant improver F-1" in the following Tables 1 to 3.
(8) Bluing Agent: (G-1) MACROLEX BLUE RR produced by LANXESS (G-2)
MACROLEX VIOLET 3R produced by LANXESS
0.00048 parts by weight of the above (G-1) and 0.00048 parts by
weight of the above (G-2) were added into the resin compositions in
all Examples and Comparative Examples.
Production of Polycarbonate Resin Composition
100 parts by weight of polycarbonate resin produced by the
interfacial polycondensation using bisphenol A and phosgene, and
prescribed amount shown in Tables 1 to 3 of phosphonium sulfonate
(A), aromatic polycarbonate resin oligomer (B), caprolactone-based
polymer (C), phosphorus-based stabilizer (D), phenol-based
antioxidant (E), weather resistant improver (F) and bluing agent
(G) were blended in a blender, and melt-kneaded by a vent-type twin
screw extruder to obtain pellets. In the blending, the following
blending method was taken because the phosphonium sulfonate (A) was
a tenacious liquid at room temperature. Namely, the tenacious
liquid of phosphonium sulfonate (A) was warmed to reduce the
viscosity, it was added to the polycarbonate resin to obtain a
pre-mixture whose phosphonium sulfonate (A) concentration was
controlled to 10% by weight by using a supermixer. Thereafter, all
materials together with the prepared pre-mixture were mixed in such
amount that the mixing ratio is controlled to the component
composition shown in Tables 1 to 3 by use of a tumbler blender. As
the vent-type twin screw extruder, "TEX30XCT" manufactured by Japan
Steel Works, Ltd., (completely intermeshing jaw type, corotaking,
double threaded type screw) was used. As the extrusion conditions,
the cylinder temperature was 280.degree. C., the extrusion rate was
25 kg/h and the screw revolution was 200 rpm.
Molding the Resin Composition
The above prepared pellets of resin-composition were dried in a
circulating hot air oven at 120.degree. for 5 hours, and thereafter
were molded to a circular disc (1) (.phi.100 mm.times.3.2 mm) and
DTUL test specimen (according to the regulation of ASTM D-648) by
use of "M150AII-SJ" type injection molding machine manufactured by
Meiki Co., Ltd. Under such conditions that the cylinder temperature
was 300.degree. C., the mold temperature was 80.degree. C. and
molding cycle time was 60 sec. Further, after residence of resin
composition in the cylinder of molding machine for 10 minutes, a
circular disc (2) was molded and used for test specimens of the
color hue measurement.
Evaluation of Molded Products
(1) Color Hue:
According to ASTM-E1925, the initial color hue/YI of circular disc
(1) having a thickness of 3.2 mm and change of color hue/YI of
circular disc before/after the residence molding (namely disc (1)
and (2))/.DELTA.YI were measured by use of a color difference meter
(SE-2000 type, manufactured by Nippon Denshoku Industries Co.,
Ltd.). The smaller the .DELTA.YI, the smaller the change of color
hue, namely the thermal color hue stability is excellent. (2) Heat
Resistance (Deflection Temperature Under Load):
According to ASTM D-648, the deflection temperature under load
(DUTL: .degree. C.) was measured under load of 1.82 MPa. (3) Total
Light Transmittance
According to ASTM D-1003, the total light transmittance of circular
disc (1) having a thickness of 3.2 mm was measured. (4) Surface
Resistance Value
According to ASTM D-257, the surface resistance value of circular
disc (1) having a thickness of 3.2 mm was measured. (5) MFR (Melt
Flow Rate)
According to JIS K 7210, the melt flow rate was measured at
temperature of 300.degree. C. under load of 1.2 kg.
TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 PC-1 100 100 100 100 100
Antistatic agent A-1 2 2 2 2 2 Oligomer B-1 1 1 1 1 1 Caprolactone
polymer C-1 0.5 1 5 7 -- Caprolactone polymer C-2 -- -- -- -- 0.3
Caprolactone polymer C-3 -- -- -- -- -- Phosphorus-based 0.1 0.1
0.1 0.1 0.1 stabilizer D-1 Antioxidant E-1 0.1 0.1 0.1 0.1 0.1
Weather resistant 0.3 0.3 0.3 0.3 0.3 improver F-1
<Evaluation> Color hue Initial color hue (YI) 0.6 0.6 0.6 0.6
0.6 Change of color hue 1.0 0.8 0.4 0.3 1.3 before/after residence
molding (.DELTA.YI) Heat resistance 125 123 118 112 126 (DTUL:
.degree. C.) Total light transmittance 89 89 89 88 89 (%) Surface
resistivity (.OMEGA.) 2 .times. 10.sup.13 2 .times. 10.sup.13 2
.times. 10.sup.13 3 .times. 10.sup.13 2 .times. 10.sup.13 MFR (g/10
min) 21 23 31 35 20
TABLE-US-00002 TABLE 2 Example 6 7 8 9 10 PC-1 100 100 100 100 100
Antistatic agent A-1 2 2 2 2 2 Oligomer B-1 1 1 1 1 1 Caprolactone
polymer C-1 -- -- -- -- -- Caprolactone polymer C-2 0.5 1 -- -- --
Caprolactone polymer C-3 -- -- 0.3 0.5 1 Phosphorus-based 0.1 0.1
0.1 0.1 0.1 stabilizer D-1 Antioxidant E-1 0.1 0.1 0.1 0.1 0.1
Weather resistant 0.3 0.3 0.3 0.3 0.3 improver F-1
<Evaluation> Color hue Initial color hue (YI) 0.6 0.6 0.6 0.6
0.6 Change of color hue 1.1 0.9 1.3 1.2 1.0 before/after residence
molding (.DELTA.YI) Heat resistance 126 125 126 126 125 (DTUL:
.degree. C.) Total light transmittance 89 89 89 88 89 (%) Surface
resistivity (.OMEGA.) 2 .times. 10.sup.13 2 .times. 10.sup.13 2
.times. 10.sup.13 2 .times. 10.sup.13 2 .times. 10.sup.13 MFR (g/10
min) 21 22 20 20 21
TABLE-US-00003 TABLE 3 Comparative Example 1 2 3 4 5 6 7 PC-1 100
100 100 100 100 100 100 Antistatic agent A-1 2 2 2 2 2 2 2 Oligomer
B-1 1 1 1 1 -- -- -- Caprolactone polymer C-1 -- 10 -- -- 1 -- --
Caprolactone polymer C-2 -- -- 10 -- -- 1 -- Caprolactone polymer
C-3 -- -- -- 10 -- -- 1 Phosphorus-based stabilizer D-1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 Antioxidant E-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Weather
resistant improver F-1 0.3 0.3 0.3 0.3 0.3 0.3 0.3
<Evaluation> Color hue Initial color hue (YI) 0.6 0.6 0.6 0.6
0.6 0.6 0.6 Change of color hue before/after 2.2 0.3 0.3 0.3 0.8
0.9 1.0 residence molding (.DELTA.YI) Heat resistance (DTUL:
.degree. C.) 127 107 108 108 125 125 125 Total light transmittance
(%) 89 87 86 86 89 89 89 Surface resistivity (.OMEGA.) 2 .times.
10.sup.13 5 .times. 10.sup.13 5 .times. 10.sup.13 5 .times.
10.sup.13 2 .times. 10.sup.13 2 .times. 10.sup.13 2 .times.
10.sup.13 MFR (g/10 min) 20 40 39 37 18 18 17
(1) Comparing with Examples and Comparative Example 1, it can be
understood that by blending the caprolactone-based polymer, the
change of color hue before/after residence molding can be prevented
and be reduced to small while maintaining the excellent heat
resistance, transparency, antistatic property and fluidity. (2)
Comparing with Examples and Comparative Examples 2 to 4, it can be
understood that by blending the caprolactone-based polymer in the
amount of 8 parts or less by weight, totally well balanced
properties in all properties of color hue before/after residence
molding, heat resistance, transparency and antistatic property can
be attained. (3) Comparing with Examples 2, 7 and 10, and
Comparative Examples 5 to 7, it can be understood that by the
aromatic polycarbonate oligomer, 20 g/10 min of MFR can be
attained, and totally well balanced properties in MFR as well as
the other properties can be attained.
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